Cation-Dependent Intrinsic Electrical Conductivity in Isostructural Tetrathiafulvalene-Based Microporous Metal–Organic Frameworks,Journal of the American Chemical Society

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Cation-Dependent Intrinsic Electrical Conductivity in Isostructural Tetrathiafulvalene-Based Microporous Metal–Organic Frameworks
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2015-01-29 , DOI: 10.1021/ja512437u
Sarah S. Park ₁ , Eric R. Hontz ₁ , Lei Sun ₁ , Christopher H. Hendon ₂ , Aron Walsh ₂ , Troy Van Voorhis ₁ , Mircea Dincă ₁

Affiliation

Isostructural metal-organic frameworks (MOFs) M2(TTFTB) (M = Mn, Co, Zn, and Cd; H4TTFTB = tetrathiafulvalene tetrabenzoate) exhibit a striking correlation between their single-crystal conductivities and the shortest S···S interaction defined by neighboring TTF cores, which inversely correlates with the ionic radius of the metal ions. The larger cations cause a pinching of the S···S contact, which is responsible for better orbital overlap between pz orbitals on neighboring S and C atoms. Density functional theory calculations show that these orbitals are critically involved in the valence band of these materials, such that modulation of the S···S distance has an important effect on band dispersion and, implicitly, on the conductivity. The Cd analogue, with the largest cation and shortest S···S contact, shows the largest electrical conductivity, σ = 2.86 (±0.53) × 10(-4) S/cm, which is also among the highest in microporous MOFs. These results describe the first demonstration of tunable intrinsic electrical conductivity in this class of materials and serve as a blueprint for controlling charge transport in MOFs with π-stacked motifs.

中文翻译：

等结构四硫富瓦烯基微孔金属-有机骨架中依赖于阳离子的本征电导率

同构金属有机骨架 (MOF) M2(TTFTB)（M = Mn、Co、Zn 和 Cd；H4TTFTB = 四硫富瓦烯四苯甲酸酯）在它们的单晶电导率和最短的 S…S 相互作用之间表现出惊人的相关性，定义为相邻的 TTF 核，与金属离子的离子半径成反比。较大的阳离子会导致 S…S 接触的收缩，这是导致相邻 S 和 C 原子上 pz 轨道之间更好的轨道重叠的原因。密度泛函理论计算表明，这些轨道与这些材料的价带密切相关，因此 S...S 距离的调制对带色散和电导率有重要影响。具有最大阳离子和最短 S…S 接触的 Cd 类似物显示出最大的电导率，σ = 2.86 (±0.53) × 10(-4) S/cm，这也是微孔 MOF 中最高的。这些结果描述了此类材料中可调本征电导率的首次证明，并作为控制具有 π 堆叠图案的 MOF 中电荷传输的蓝图。

更新日期：2015-01-29

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